Polymerization process for producing ethylene based polymers

Abstract

The instant invention provides a polymerization process for producing ethylene based polymers. In one embodiment, the instant invention provides a polymerization process for producing ethylene based polymers comprising: polymerizing ethylene with optionally one or more α-olefins in the presence of one or more first catalyst systems and optionally one or more second catalyst systems in a single reactor, wherein first catalyst system comprises; (a) one ore more procatalysts comprising a metal-ligand complex of formula (I):

We claim: 
     
       1. A polymerization process for producing ethylene based polymers comprising:
 polymerizing ethylene and optionally one or more α-olefins in the presence of one or more first catalyst systems and optionally one or more second catalyst systems in a single reactor, wherein first catalyst system comprises; 
 (a) one or more procatalysts comprising a metal-ligand complex of formula (I): 
 
       
         
           
           
               
               
           
         
         wherein: 
         M is titanium, zirconium, or hafnium, each independently being in a formal oxidation state of +2, +3, or +4; and n is an integer of from 0 to 3, and wherein when n is 0, X is absent; and each X independently is a monodentate ligand that is neutral, monoanionic, or dianionic; or two Xs are taken together to form a bidentate ligand that is neutral, monoanionic, or dianionic; and X and n are chosen in such a way that the metal-ligand complex of formula (I) is, overall, neutral; and L is (C 3 -C 40 )hydrocarbylene or (C 3 -C 40 )heterohydrocarbylene; and 
         each R 1a  and each R 1b  is independently (C 1 -C 40 )hydrocarbyl; (C 1 -C 40 )heterohydrocarbyl; Si(R C ) 3 , Ge(R C ) 3 , P(R P ) 2 , N(R N ) 2 , OR C , SR C , NO 2 , CN, CF 3 , R C S(O)—, R C S(O) 2 —, (R C ) 2 C═N—, R C C(O)O—, R C OC(O)—, R C C(O)N(R)—, (R C ) 2 NC(O)—, halogen atom, 
         R 3 , R 6 , R 8 , R 9 , R 11 , and R 14  are independently selected from the group consisting of a (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, Si(R C ) 3 , Ge(R C ) 3 , P(R P ) 2 , N(R N ) 2 , OR C , SR C , NO 2 , CN, CF 3 , R C S(O)—, R C S(O) 2 —, (R C ) 2 C═N—, R C C(O)O—, R C OC(O)—, R C C(O)N(R)—, (R C ) 2 NC(O)—, halogen atom, hydrogen atom, and combinations thereof; 
         when R 8  is H, R 9  is a (C 1 -C 40 )hydrocarbyl; (C 1 -C 40 )heterohydrocarbyl; Si(R C ) 3 , Ge(R C ) 3 , P(R P ) 2 , N(R N ) 2 , OR C , SR C , NO 2 , CN, CF 3 , R C S(O)—, R C S(O) 2 —, (R C ) 2 C═N—, R C C(O)O—, R C OC(O)—, R C C(O)N(R)—, (R C ) 2 NC(O)— or halogen atom; or 
         when R 9  is H, R 8  is a (C 1 -C 40 )hydrocarbyl; (C 1 -C 40 )heterohydrocarbyl; Si(R C ) 3 , Ge(R C ) 3 , P(R P ) 2 , N(R N ) 2 , OR C , SR C , NO 2 , CN, CF 3 , R C S(O)—, R C S(O) 2 —, (R C ) 2 C═N—, R C C(O)O—, R C OC(O)—, R C C(O)N(R)—, (R C ) 2 NC(O)— or halogen atom; wherein each R C , each R N , and each R P  is independently (C 1 -C 30 )hydrocarbyl, and 
         optionally two or more the R 3 , R 6 , R 8 , R 9 , R 11 , and R 14  groups can combine together into ring structures, with such ring structures having from 3 to 50 atoms in the ring excluding any hydrogen atoms; 
         each of the hydrocarbyl, heterohydrocarbyl, Si(R C ) 3 , Ge(R C ) 3 , P(R P ) 2 , N(R N ) 2 , OR C , SR C , R C S(O)—, R C S(O) 2 —, (R C ) 2 C═N—, R C C(O)O—, R C OC(O)—, R C C(O)N(R)—, (R C ) 2 NC(O)—, hydrocarbylene, and heterohydrocarbylene groups independently is unsubstituted or substituted with one or more R S  substituents; 
         each R S  independently is a halogen atom, polyfluoro substitution, perfluoro substitution, unsubstituted (C 1 -C 18 )alkyl, F 3 C—, FCH 2 O—, F 2 HCO—, F 3 CO—, R 3 Si—, R 3 Ge—, RO—, RS—, RS(O)—, RS(O) 2 —, R 2 P—, R 2 N—, R 2 C═N—, NC—, RC(O)O—, ROC(O)—, RC(O)N(R)—, or R 2 NC(O)—, or two of the R S  are taken together to form an unsubstituted (C 1 -C 18 )alkylene, wherein each R independently is an unsubstituted (C 1 -C 18 )alkyl; and 
         (b) one or more cocatalysts; wherein the ratio of total number of moles of the one or more metal-ligand complexes of formula (I) to total number of moles of the one or more cocatalysts is from 1:10,000 to 100:1. 
       
     
     
       2. The polymerization process according to  claim 1 , wherein R 3  and R 14  are independently chosen from tert-octyl or tert-butyl. 
     
     
       3. The polymerization process according to  claim 1 , wherein R 8  and R 9  are independently chosen from methyl, ethyl, 2-propyl, chloro, fluoro, or —NMe 2 . 
     
     
       4. The polymerization process according to  claim 1 , wherein R 6  and R 11  are independently chosen from methyl, chloro, or fluoro. 
     
     
       5. The polymerization process according to  claim 1 , wherein each R 1a  and each R 1b  is independently chosen tert-butyl, n-propyl, 2-propyl, —SiMe 3 , —Si(Me) 2 tBu, 3,5-di-tert-butylphenyl, 3,5-di-methylphenyl, or phenyl. 
     
     
       6. The polymerization process according to  claim 1 , wherein each R 1a  and each R 1b  is tert-butyl. 
     
     
       7. The polymerization process according to  claim 1 , wherein each R 1a  and each R 1b  are tert-butyl; R 3  and R 14  are tert-octyl; R 6  and R 11  are fluoro; R 8  is hydrogen; and R 9  is methyl. 
     
     
       8. The polymerization process according to  claim 1 , wherein each R 1a  and each R 1b  are tert-butyl; R 3  and R 14  are tert-octyl; R 6  and R 11  are fluoro; and R 8  and R 9  are methyl. 
     
     
       9. The polymerization process according to  claim 1 , wherein each R 1a  and each R 1b  are tert-butyl; R 3  and R 14  are tert-octyl; R 6  and R 11  are fluoro; R 8  and R 9  are methyl; and L is —CH 2 Si(Et) 2 CH_—. 
     
     
       10. The polymerization process according to  claim 1 , wherein each R 1a  and each R 1b  are tert-butyl; R 3  and R 14  are tert-octyl; R 6  and R 11  are fluoro; R 8  is hydrogen; R 9  is methyl; and L is —CH 2 Si(Et) 2 CH 2 —.